CN102925052A - Double-curing vacuum plating UV (Ultraviolet) coating finish - Google Patents
Double-curing vacuum plating UV (Ultraviolet) coating finish Download PDFInfo
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- CN102925052A CN102925052A CN2012104593168A CN201210459316A CN102925052A CN 102925052 A CN102925052 A CN 102925052A CN 2012104593168 A CN2012104593168 A CN 2012104593168A CN 201210459316 A CN201210459316 A CN 201210459316A CN 102925052 A CN102925052 A CN 102925052A
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- dope
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Abstract
The invention relates to double-curing vacuum plating UV (Ultraviolet) coating finish. Hydroxyl polyurethane acrylate with a high functional group and hydroxyl polyurethane acrylate with a low functional group are used as main components, a photoinitiator and isocyanate are used as curing agents, a wetting dispersant and a flatting agent are used as auxiliary materials, inorganic fillers are mixed, a solvent is used as a viscosity modifier, and all the components are mixed to prepare the double-curing vacuum plating UV coating finish. The product is widely applied to adornment of goods including plastic electronic products such as mobile phones and electrical equipment, as well as cosmetic boxes, automobile lamp cups and the like.
Description
Technical field
The present invention relates to coating, particularly the finish paint of the decorative paint of the plastic electronic such as mobile phone, electrical equipment product, cosmetic packaging box, automobile lamp etc.
Background technology
Technique for vacuum coating is called again vacuum plating process, refers under vacuum environment, and certain metal or metallic compound are deposited to material surface (normally non-metallic material) with the form of gas, belongs to physical gas-phase deposition (PVD).Vacuum plating UV photo-cured coating method is: will evaporation object such as plastics or film etc.; place in the high vacuum chamber; by the METAL HEATING PROCESS such as aluminium, tin, indium, copper being made it evaporation; metallic vapor with average free conduct scattering, cool off and be attached to by on the evaporation thing surface; form metallic film; make article surface have metal sense outward appearance, protect at its surface spraying UV photo-cured coating photo-cured coating again.The vacuum plating UV photo-cured coating mainly is comprised of light trigger, reactive monomer and oligopolymer.The UV photo-cured coating is through UV-irradiation, light-initiated generation living radical, and then initiating activity monomer and living oligomer radical polymerization, crosslinked the not melting property solid film that is converted into.
The UV photo-cured coating is ultraviolet-curing paint, ultraviolet-curing paint is after UV-irradiation, light trigger absorbing ultraviolet optical radiation energy and being activated at first, its molecule out-shell electron jumps, within the extremely short time, generate the active centre, the then unsaturated group effect in active centre and the resin, the two keys that cause in light-cured resin and the reactive thinner molecule disconnect, generation successive polymerization reaction, thereby the film forming of being cross-linked with each other.Chemical kinetics studies show that UV-light impels the mechanism of UV paint solidification to belong to free radical chain reaction polymerization.It at first is the light-initiated stage; Next is the transfer reaction stage, and this one-phase is along with the carrying out of chainpropagation, and system can occur crosslinked, film-forming; Last chain free radical can be finished chain termination by coupling or disproportionation.
At present, the market conventional vacuum is electroplated just one-step forming of UV photo-cured coating, and namely conventional vacuum is electroplated on the basis of UV photo-cured coating, introduction contains-NCO and-reaction of OH, reach both UV curable, again heat-setting effect, i.e. dual cure vacuum plating UV photo-cured coating.The dual cure theory refers to when common UV photo-cured coating is by the light trigger initiated polymerization, by the hydroxyl in the resin and the isocyanate group polymerization reaction take place in the solidifying agent, is beneficial to raising system sticking power and over-all properties.
In the prior art, common curing form and vacuum plating UV photo-cured coating solidify and can not mutually coexist.Usually ,-NCO group and-polymeric acceptor that the OH group generates by crosslinking reaction ties up to stability and aspect of performance, the polymeric system that does not all generate by ultraviolet light polymerization effective.Such as patent application 201110009627.X disclosed " a kind of mobile phone vacuum plating ultraviolet-curing paint ", it is to be made of finish paint and priming paint, and wherein finish paint is to contain solvent-borne type oligopolymer, Dipentaerythritol five acrylate, 1-Methoxy-2-propyl acetate (PMA), pure acid butyl ester, ethyl glycolate, toluene, flow agent and light trigger by aliphatic polyurethane six acrylate, acrylate upgrading to be mixed; Priming paint then is to be made by the ultraviolet curing oligopolymer of urethane acrylate, Dipentaerythritol five acrylate, Viscoat 295, pentaerythritol triacrylate, the third oxidation neopentylglycol diacrylate, Resins, epoxy, pure acid butyl ester, ethyl glycolate, toluene, flow agent and light trigger.Obviously this coating is by the employed ultraviolet-curing paint of common solidifying agent, is not the vacuum plating UV photo-cured coating with dual cure effect, can't reach the effect of ultraviolet light polymerization and thermofixation.
Summary of the invention
The object of the present invention is to provide a kind of vacuum plating UV dope finish paint of dual cure, guarantee sticking power when having solved vacuum plating UV photo-cured coating high rigidity, high ethanol-tolerant, high abrasion and high water boiling resistance.
Another object of the present invention provides a kind of high-performance dual cure vacuum plating UV dope and preparation method thereof, this coating application technique is identical with traditional vacuum plating UV photo-cured coating technique, be easy to realize, manufacture conveniently, with low cost, only need add the solidifying agent of respective amount before the finish paint spraying.
For achieving the above object, the present invention realizes (in the following description, unless stated otherwise, the proportioning of each component and mixture is weight ratio) by following technique means.
A kind of vacuum plating UV dope finish paint of dual cure, it is to be mixed by following component: in weight ratio, the high functional group urethane acrylate of hydroxyl 20-50 part, hydroxyl hangs down functional group urethane acrylate 20-40 part, initiator 3-8 part, isocyanic ester 2-5 part, wetting dispersing agent 0-0.5 part, flow agent 0-1 part, mineral filler 1-10 part; Solvent 10-30 part.
Described solvent is the mixture of acrylate-functional reactive monomer and thinner, and wherein the usage ratio of acrylate-functional reactive monomer and thinner is 1:1.
As preferably, described functional vinylformic acid reactive monomer is the tripropylene glycol double methacrylate, described thinner is mixed solvent, mixed solvent is that the ratio of 5:2:3 mixes by the solvent three of ester class, ketone, alcohols according to weight ratio, and the consumption of tripropylene glycol double methacrylate and mixed solvent is: tripropylene glycol double methacrylate: mixed solvent=1:1.
As preferably, described initiator is selected 1-hydroxy-cyclohexyl phenyl ketone and the basic formyl radical diphenyl phosphine oxide of 2,4,6-front three, and wherein, by weight, 1-hydroxy-cyclohexyl phenyl ketone is 2-5 part; TMDPO 1-3 part.
As preferably, described wetting dispersing agent is the unsaturated polycarboxylic acid polymers soln of lower molecular weight, and flow agent is polyether-modified polydimethylsiloxane.
The high functional group urethane acrylate of described hydroxyl is that the functional group urethane acrylate is two functional group hydroxyl polyurethane acrylate at the bottom of six functionality urethane acrylates, the hydroxyl.
In order to produce the vacuum plating UV dope finish paint of this high performance dual cure, its making method comprises that step is as follows:
(1), batching:
Stirred opening scuffing of cylinder bore (palpus cleaning, clean, pollution-free) at certain capacity feeds intake according to formula rate and turnout; In light trigger, partial solvent input cylinder, soak after 10-15 minute;
(2) dispersed with stirring:
After finishing, batching continues to feed intake, the high functional group urethane acrylate of adding hydroxyl, the low functional group urethane acrylate of hydroxyl, wetting dispersing agent (adopting poly-hydroxyl dimethyl silica), flow agent are that polyether-modified polydimethylsiloxane, functional vinylformic acid reactive monomer adopt the tripropylene glycol double methacrylate, and mineral filler.Material has been thrown in the rear employing pan mixer device and had been hastened to disperse 5-10 minute, visually stirs fully, and be normal if any the white foam phenomenon;
(3) adjust: the coating that disperses to finish by adding remaining solvent cut, is transferred to 8.5s with viscosity, proportionally adds again isocyanic ester, use 400 order filter-cloth filterings, the vacuum plating UV dope finish paint of dual cure.
Solidify: sprayed product on base material, first through the temperature baking, again through ultraviolet curing, new surperficial paint film effect after namely formation is solidified.
The vacuum plating UV dope finish paint of this dual cure, take high-performance hydroxyl polyurethane CALCIUM ACRYLATE as main component, take light trigger and isocyanic ester as solidifying agent, take wetting dispersing agent, flow agent as auxiliary material, be mixed with mineral filler, make as viscosity modifier mixes take acrylate-functional reactive monomer or mixed solvent.This coating needs to add solidifying agent before the finish paint spraying, in use, need through dual cure: namely through temperature baking and ultraviolet light polymerization.The technique of this invention is identical with traditional vacuum plating UV photo-cured coating technique, and this coating is can generation property good, gloss is high, the good texts of fullness ratio, realizes the requirements such as hardness is high, sticking power is fabulous.Enriched the installing effect of the field surface coatingss such as plastic electronic product, minaudiere, automobile lamp such as mobile phone, electrical equipment.
Through verification experimental verification, the vacuum plating UV dope finish paint of the dual cure of made of the present invention, its sticking power test (3M adhesive tape, the test of hundred lattice) is 4B; Anti-alcohol test (99.5% ethanol) is 2000 times/1000g power; Wear-resisting test: paper tape wear-resisting (NORMAN RCA) is 800 times; Hardness test: the pencil 1Kgf 2H of Mitsubishi surface is without obvious cut; Water boiling resistance (100 ° of C boiling water) is 4 hours, does not come off.
Embodiment
The invention will be further described below in conjunction with embodiment, but should understand these embodiment limits the scope of the invention, in the situation of the spirit and scope of the present invention, those skilled in the art can make changes and improvements so that it is fit to different service conditions, condition and embodiment to the present invention.
The vacuum plating UV dope finish paint of the high-performance dual cure that the present invention realizes, it is take high ductibility, photochemistry property polyurethane acrylic resin as main component, take environment-friendly type ultraviolet initiator and isocyanic ester as solidifying agent, take wetting dispersing agent, flow agent etc. as auxiliary material, be mixed with mineral filler, take functional CALCIUM ACRYLATE reactive monomer and solvent as viscosity modifier.The weight proportion of its each component is as follows: the high functional group urethane acrylate of hydroxyl: 20-50 part; Hydroxyl hangs down functional group urethane acrylate 20-40 part: initiator 3-8 part, isocyanic ester agent 2-5 part; Wetting dispersing agent 0-0.5 part; Flow agent 0-1 part; Mineral filler: 1-10 part; Solvent (acrylate-functional reactive monomer or thinner) 10-30 part.
Production technique comprises the three phases such as batching, dispersion, adjustment.And curing is the mode that adopts dual cure, that is: thermofixation and ultraviolet light polymerization.Wherein, the heat curing temperature scope is at 60-70 ℃, and the time is 10-20 minute; The ultraviolet light polymerization fluorescent tube is to adopt 3 80-120W/cm high voltage mercury lamp radiation branchings, and 6 80-120W/cm high voltage mercury lamp radiations solidify.
Wherein, the high functional group urethane acrylate of described hydroxyl is that the functional group urethane acrylate is two functional group hydroxyl polyurethane acrylate at the bottom of six functionality urethane acrylates, the hydroxyl, preliminary election takes into account the product of the physical property such as snappiness is good, gloss is high, sticking power is good, range of viscosities 5,000-15,000mPas/30 ℃.
Initiator is: 1-hydroxy-cyclohexyl phenyl ketone 2-5 part; TMDPO 1-3 part.
Wetting dispersing agent is the unsaturated polycarboxylic acid polymkeric substance of lower molecular weight.
Flow agent is polyether-modified polydimethylsiloxane.
Wherein, mineral filler is little wax powder (nano level).
Wherein, solvent is functional vinylformic acid reactive monomer and thinner, they are selected from respectively Viscoat 295 and mixed solvent (ester class, ketone, alcohols three mix ratio 5:2:3), Viscoat 295: the usage ratio=1:1 of mixed solvent.
Embodiment one.
(1), batching:
(wherein 1-hydroxy-cyclohexyl phenyl ketone is 2 parts with 3 parts of 4 parts of mixed solvents, the agent of drawing of light at the stirred opening scuffing of cylinder bore of certain capacity (must cleaning, clean, pollution-free); 1 part of TMDPO) in the input cylinder, soak after 10-15 minute.
(2) dispersed with stirring:
After batching is finished, add 20 parts of the high functional group urethane acrylates of hydroxyl, 20 parts of the low functional group urethane acrylates of hydroxyl, 5 parts of Viscoat 295s, 1 part of mineral filler.Adopt to hasten to disperse in the pan mixer device 5-10 minute, visual stirring fully obtains Ji Mo (if any the white foam phenomenon for normal) again.
(3) adjust: the base China ink that disperses to finish by adding remaining 1 part of mixed solvent dilution, is transferred to 8.5s with viscosity, adds again 2 parts of isocyanic ester, use 400 order filter-cloth filterings, the vacuum plating UV dope finish paint of dual cure.
Need be cured during use: sprayed product on base material through temperature baking, ultraviolet curing, namely forms the surperficial paint film effect of dual cure UV coating after solidifying.
Embodiment two.
(1), batching:
(wherein 1-hydroxy-cyclohexyl phenyl ketone is 4 parts with 6 parts of 6 parts of mixed solvents, the agent of drawing of light at the stirred opening scuffing of cylinder bore of certain capacity (must cleaning, clean, pollution-free); 2 parts of TMDPOs) in the input cylinder, soak after 10-15 minute.
(2) dispersed with stirring:
After batching is finished, add 35 parts of the high functional group urethane acrylates of hydroxyl, 30 parts of the low functional group urethane acrylates of hydroxyl, 0.3 part of wetting agent, 0.5 part of flow agent, 10 parts of functional vinylformic acid reactive monomers, 5 parts of mineral fillers.Adopt to hasten to disperse in the pan mixer device 5-10 minute, visual stirring fully obtains Ji Mo (if any the white foam phenomenon for normal) again.
(3) adjust: the base China ink that disperses to finish by adding 4 parts of mixed solvents dilutions, is transferred to 8.5s with viscosity, adds again 4 parts of isocyanic ester, use 400 order filter-cloth filterings, finished product.
Solidify: sprayed product on base material through temperature baking, ultraviolet curing, namely forms the surperficial paint film effect of dual cure UV coating after solidifying.
Embodiment three.
(1), batching:
(wherein 1-hydroxy-cyclohexyl phenyl ketone is 5 parts with 8 parts of 10 parts of solvents, the agent of drawing of light at the stirred opening scuffing of cylinder bore of certain capacity (must cleaning, clean, pollution-free); 3 parts of TMDPOs) in the input cylinder, soak after 10-15 minute.
(2) dispersed with stirring:
After batching is finished, add 45 parts of the high functional group urethane acrylates of hydroxyl, 40 parts of the low functional group urethane acrylates of hydroxyl, 0.5 part of wetting agent, 1 part of flow agent, 15 parts of functional vinylformic acid reactive monomers, 10 parts of mineral fillers.Adopt to hasten to disperse in the pan mixer device 5-10 minute, visual stirring fully obtains Ji Mo (if any the white foam phenomenon for normal) again.
(3) adjust: the base China ink that disperses to finish by adding 5 parts of mixed solvents dilutions, is transferred to 8.5s with viscosity, adds again 5 parts of isocyanic ester, use 400 order filter-cloth filterings, finished product.
Solidify: sprayed product on base material through temperature baking, ultraviolet curing, namely forms the surperficial paint film effect of dual cure UV coating after solidifying.
It is as follows that the vacuum plating UV dope finish paint of this dual cure reaches performance index.
Sticking power test (3M adhesive tape, the test of hundred lattice): 4B.
Anti-alcohol test (99.5% ethanol): 2000 times/1000g power.
Wear-resisting test, paper tape wear-resisting (NORMAN RCA): 800 times.
Hand perspiration test: PH4.7-PH10.2 normal temperature 24 hours.
Hardness test: the pencil 1Kgf 2H of Mitsubishi surface is without obvious cut.
Water boiling resistance (100 ° of C boiling water): 4 hours, do not come off.
Bending test 120 degree are without the brittle failure phenomenon.
High-temperature storage relative temperature 60
+2 degree, relative humidity 95% product surface is without unusually.
Low-temperature storage-30
+3 degree, product appearance is without unusually.
The present invention can be by the viscosity of acrylate-functional reactive monomer and mixed solvent adjusting coating, to adapt to the needs of different sprayings.
In sum, the new surface effect of the present invention sprays dual cure UV coating in addition to the implementation, and the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (6)
1. the vacuum plating UV dope finish paint of a dual cure, it is characterized in that this finish paint is to be mixed by following component: in weight ratio, the high functional group urethane acrylate of hydroxyl 20-50 part, hydroxyl hangs down functional group urethane acrylate 20-40 part, initiator 3-8 part, isocyanic ester 2-5 part, wetting dispersing agent 0-0.5 part, flow agent 0-1 part, mineral filler 1-10 part; Solvent 10-30 part.
2. the vacuum plating UV dope finish paint of dual cure according to claim 1, it is characterized in that described solvent is the mixture of acrylate-functional reactive monomer and thinner, wherein the usage ratio of acrylate-functional reactive monomer and thinner is 1:1.
3. the vacuum plating UV dope finish paint of dual cure according to claim 2, it is characterized in that as preferred, described functional vinylformic acid reactive monomer is the tripropylene glycol double methacrylate, described thinner is mixed solvent, mixed solvent is that the ratio of 5:2:3 mixes by the solvent three of ester class, ketone, alcohols according to weight ratio, and the consumption of tripropylene glycol double methacrylate and mixed solvent is tripropylene glycol double methacrylate: mixed solvent=1:1.
4. the vacuum plating UV dope finish paint of dual cure according to claim 1 is characterized in that described initiator selects 1-hydroxy-cyclohexyl phenyl ketone and 2,4, the basic formyl radical diphenyl phosphine oxide of 6-front three, wherein, by weight, 1-hydroxy-cyclohexyl phenyl ketone is 2-5 part; TMDPO 1-3 part.
5. the vacuum plating UV dope finish paint of dual cure according to claim 1 is characterized in that described wetting dispersing agent is the unsaturated polycarboxylic acid polymers soln of lower molecular weight, and flow agent is polyether-modified polydimethylsiloxane.
6. the vacuum plating UV dope finish paint of dual cure according to claim 1 is characterized in that the high functional group urethane acrylate of described hydroxyl is that the functional group urethane acrylate is two functional group hydroxyl polyurethane acrylate at the bottom of six functionality urethane acrylates, the hydroxyl.
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| CN201210459316.8A CN102925052B (en) | 2012-11-15 | 2012-11-15 | Double-curing vacuum plating UV (Ultraviolet) coating finish |
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| CN201210459316.8A CN102925052B (en) | 2012-11-15 | 2012-11-15 | Double-curing vacuum plating UV (Ultraviolet) coating finish |
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| CN104293162A (en) * | 2014-09-16 | 2015-01-21 | 安徽宏浩涂料有限公司 | Dual photocurable UV (ultraviolet) paint as well as preparation method and spraying method thereof |
| CN104449334A (en) * | 2014-12-03 | 2015-03-25 | 珠海东诚光固化材料有限公司 | Fluorocarbon coating and method for preparing colored aluminum profiles from fluorocarbon coating |
| CN104673020A (en) * | 2015-03-05 | 2015-06-03 | 廊坊立邦涂料有限公司 | Single-coating, high-gloss and boiling-resisting plastic paint and preparation method thereof |
| CN106366901A (en) * | 2016-08-27 | 2017-02-01 | 彩城（惠州）化工有限公司 | Doubly solidified coloring UV nanometer paint |
| CN109280477A (en) * | 2018-09-18 | 2019-01-29 | 芜湖春风新材料有限公司 | A kind of preparation method of coloured dual cure UV coating |
| CN109762421A (en) * | 2018-12-26 | 2019-05-17 | 宁波惠之星新材料科技有限公司 | A kind of curved surface cover board hardening masking liquid and the method for preparing curved surface cover board hardening coat using the masking liquid |
| CN110157325A (en) * | 2019-05-31 | 2019-08-23 | 绵阳彩馥兰科技有限责任公司 | A kind of water fever light dual-cured coating |
| CN111471337A (en) * | 2019-12-16 | 2020-07-31 | 广东一纳科技有限公司 | Composition, preparation method and application in field of anticorrosive coating |
| CN114479630A (en) * | 2021-12-27 | 2022-05-13 | 有沣(厦门)实业有限公司 | Multicolor vacuum plating formula |
| CN114773987A (en) * | 2022-06-09 | 2022-07-22 | 南通康尔乐复合材料有限公司 | Stretchable UV hardening liquid for automobile decoration film and preparation method of hardened PC (polycarbonate) using stretchable UV hardening liquid |
| CN115785792A (en) * | 2022-11-10 | 2023-03-14 | 嘉兴敏惠汽车零部件有限公司 | Photocuring colored finish paint for protecting PVD (physical vapor deposition) indium plating of automobile exterior trimming parts and preparation method thereof |
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Cited By (15)
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| CN104293162A (en) * | 2014-09-16 | 2015-01-21 | 安徽宏浩涂料有限公司 | Dual photocurable UV (ultraviolet) paint as well as preparation method and spraying method thereof |
| CN104449334A (en) * | 2014-12-03 | 2015-03-25 | 珠海东诚光固化材料有限公司 | Fluorocarbon coating and method for preparing colored aluminum profiles from fluorocarbon coating |
| CN104673020A (en) * | 2015-03-05 | 2015-06-03 | 廊坊立邦涂料有限公司 | Single-coating, high-gloss and boiling-resisting plastic paint and preparation method thereof |
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| CN109280477A (en) * | 2018-09-18 | 2019-01-29 | 芜湖春风新材料有限公司 | A kind of preparation method of coloured dual cure UV coating |
| CN109762421A (en) * | 2018-12-26 | 2019-05-17 | 宁波惠之星新材料科技有限公司 | A kind of curved surface cover board hardening masking liquid and the method for preparing curved surface cover board hardening coat using the masking liquid |
| CN110157325A (en) * | 2019-05-31 | 2019-08-23 | 绵阳彩馥兰科技有限责任公司 | A kind of water fever light dual-cured coating |
| CN111471337A (en) * | 2019-12-16 | 2020-07-31 | 广东一纳科技有限公司 | Composition, preparation method and application in field of anticorrosive coating |
| CN114479630A (en) * | 2021-12-27 | 2022-05-13 | 有沣(厦门)实业有限公司 | Multicolor vacuum plating formula |
| CN114773987A (en) * | 2022-06-09 | 2022-07-22 | 南通康尔乐复合材料有限公司 | Stretchable UV hardening liquid for automobile decoration film and preparation method of hardened PC (polycarbonate) using stretchable UV hardening liquid |
| CN114773987B (en) * | 2022-06-09 | 2023-03-28 | 南通康尔乐复合材料有限公司 | Stretchable UV hardening liquid for automobile decoration film and preparation method of hardened PC (polycarbonate) using stretchable UV hardening liquid |
| CN115785792A (en) * | 2022-11-10 | 2023-03-14 | 嘉兴敏惠汽车零部件有限公司 | Photocuring colored finish paint for protecting PVD (physical vapor deposition) indium plating of automobile exterior trimming parts and preparation method thereof |
| CN116515351A (en) * | 2023-04-19 | 2023-08-01 | 中南机诚精密制品(深圳)有限公司 | Preparation method of alloy product and micro-arc oxidation layer added with one paint composite film layer |
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